Benzothiazolones, and their production and use

ABSTRACT

A compound of the formula: ##STR1## wherein R is a hydrogen atom, a C 1  -C 5  alkyl group, a C 3  -C 4  alkenyl group, a C 3  -C 4  alkynyl group, a halo(C 1  -C 4 )alkyl group, a halo(C 3  -C 4 )alkenyl group, a halo(C 3  -C 4 )alkynyl group, a C 1  -C 2  alkoxy(C 1  -C 2 ) alkyl group, a C 1  -C 2  alkoxy(C 1  -C 2 )alkoxy(C 1  -C 2 )alkyl group, a cinnamyl group, a cyano(C 1  -C 3 )alkyl group, a carboxy(C 1  -C 3 )alkyl group, a C 1  -C 5  alkoxycarbonyl(C 1  -C 3 )alkyl group, a halo(C 1  -C 5 )alkoxycarbonyl(C 1  -C 3 )alkyl group, a C 1  -C 2  alkoxyalkoxycarbonyl(C.sub. 1 -C 3 )alkyl group, a C 1  -C 2  alkoxy (C 1  -C 2 )alkoxycarbonyl(C 1  -C 3 )alkyl group, a C 1  -C 5  alkoxycarbonyl(C 1  -C 2 )-alkoxycarbonyl(C 1  -C 3 )alkyl group, a cyclo(C 3  -C 6 )alkoxycarbonyl(C 1  -C 3 )alkyl group, a C 1  -C 5  alkylaminocarbonyl(C 1  -C 3 )alkyl group or a di-(C 1  -C 5 )alkylaminocarbonyl(C 1  -C 3 )alkyl group and A is an amino group or a nitro group, is disclosed. These compounds are useful as intermediates in the synthetic of benzothiazolone herbicides.

This application is a division of copending application Ser. No.911,360, filed on Sept. 25, 1986, now U.S. Pat. No. 4,720,297.

The present invention relates to benzothiazolones, and their productionand use. More particularly, the invention relates to novelbenzothiazolones, a process for producing them, and their use asherbicides.

Some benzothiazolone derivatives (e.g.4-chloro2,3-dihydro-2-oxobenzothiazol-3-ylacetic acid (benazolin)) areknown to be effective as herbicides [Herbicide Handbook of the WeedScience Society of America, 5th Ed., p. 40 (1983)]. However, theirherbicidal activity is not necessarily satisfactory.

It has now been found that the benzothiazolones of the formula: ##STR2##wherein R is a hydrogen atom, a C₁ -C₅ alkyl group, a C₃ -C₄ alkenylgroup, a C₃ -C₄ alkynyl group, halo(C₁ -C₄)alkyl group, a halo(C₃-C₄)alkenyl group, a halo(C₃ -C₄)alkynyl group, a C₁ -C₂ alkoxy(C₁-C₂)alkyl group, a C₁ -C₂ alkoxy(C₁ -C₂)alkoxy(C₁ -C₂)alkyl group, acinnamyl group, a cyano(C₁ -C₃)alkyl group, a carboxy(C₁ -C₃)alkylgroup, a C₁ -C₅ alkoxycarbonyl(C₁ -C₃)alkyl group, a halo( C₁-C₅)alkoxycarbonyl(C₁ -C₃)alkyl group, a C₁ -C₂ alkoxy(C₁-C₂)alkloxycarbonyl(C₁ -C₃)alkyl group, a C₁ -C₅ alkoxycarbonyl(C₁-C₂)alkoxycarbonyl(C₁ -C₃)alkyl group, a cyclo(C₃ -C₆)alkoxycarbonyl(C₁-C₃)alkyl group, a C₁ -C₅ alkylaminocarbonyl(C₁ -C₃)alkyl group or adi(C₁ -C₅)alkylaminocarbonyl(C₁ -C₃)alkyl group exhibit a highherbicidal activity against a wide variety of weeds includingbroad-leaved weeds, Graminaceous weeds, Commelinaceous weeds andCyperaceous weeds in agricultural plowed field by foliar or soiltreatment without producing any material phytotoxicity on variousagricultural crops such as corn, sorghum, wheat, barley, soybean, peanutand cotton. Examples of the broad-leaved weeds are wild buckwheat(Polygonum convolvulus), ladysthumb (Polygonum pessicaria), palesmartweed (Polygonum lapathifolium), common purslane (Portulacaoleracea), common chickweed (Stellaria media), common lambsquarters(Chenopodium album), redroot pigweed (Amaranthus retroflexus), radish(Raphanus sativus), wild mustard (Sinapis arvensis), shepherdspurse(Capsella bursa-pastoris), hemp sesbania (Sesbania exaltata), sicklepod(Cassia obtusifolia), velvetleaf (Abutilon theophrasti), prickly sida(Sida spinosa), field pansy (Viola arvensis), catchweed bedstraw (Galiumaparine), ivyleaf morningglory (Ipomoea hederacea), tall morningglory(Ipomoea purpurea), field bindweed (Convolvulus arvensis), jimsonweed(Datura stramonium), black nightshade (Solanum nigrum), persianspeedwell (Veronica persica), common cocklebur (Xanthium pensylvanicum),common sunflower (Helianthus annuus), scentless chamomile (Matricariaperforata), corn marigold (Chrysanthemum segetum), sun spurge (Euphorbiahelioscopia), etc. Examples of Graminaceous weeds are Japanese millet(Echinochloa frumentacea), barnyardgrass (Echinochloa crus-galli),sicklepod (Cassia obtusifolia), large crabgrass (Digitaria sangunialis),annual bluegrass (Posa annua), blackgrass (Alopercurus myosuroides),oats (Avena sativa), wild oats (Avena fatua), johnsongrass (Sorghumhalepense), quackgrass (Agropyron repens), downy brome (Bromustectorum), bermudagrass (Cynodon dactylon), fall panicum (Panicumdichotomiflorum), etc. Examples of Commelinaceous weeds are asiaticdayflower (Commelina communis), etc. Examples of the Cyperaceous weedsare rice flatsedge (Cyperus iria), etc.

Particularly, it is notable that the benzothiazolones (I) exert aprominent herbicidal activity by soil application before germination ofundesired weeds with no material chemical injury. For instance, theyshow a high herbicidal potency on the broad-leaved weeds such asvelvetleaf, common cocklebur, tall morningglory, sicklepod, pricklysida, jimsonweed, hemp sesbania, reedroot pigweed, common lambsquarters,and black nightshade in a field of corn but afford no materialphytotoxicity to corn. In a field of sorghum, they exhibit an excellentherbicidal activity on broad-leaved weeds such as redroot pigweed,velvetleaf, ivyleaf morningglory, tall morningglory and common cockleburas well as Graminaceous weeds such as johnsongrass, but exert nochemical injury on sorghum. Undesired broad-leaved weeds such ascatchweed bedstraw, common chickweed, field pansy, persion speedwell,scentless chamomile, pale smartweed, wild mustard, common lambsquarters,black nightshade and field bindweed and redroot pigweed in a field ofwheat or barley can likewise be sufficiently controlled without exertingany material phytotoxicity to wheat or barley. Problematic broad-leavedweeds in a fields of soybeans or peanuts such as velvetleaf, commoncocklebur, tall morningglory, sicklepod, prickly sida, jimsonweed, hempsesbania, redroot pigweed, common lambsquarters and black nightshade canalso be controlled with no material phytotoxicity to the soybeans orpeanuts. Further, they are highly effective in controlling thebroad-leaved weeds such as redroot pigweed, prickly sida, ivyleafmorningglory, tall morningglory, black nightshade and common cockleburin a field of cotton without causing any material chemical injury tocotton.

The benzothiazolones (I) of the invention are also effective inexterminating the paddy field weeds including Graminaceous weeds such asbarnyardgrass (Echinochloa oryzicola), broad-leaved weeds such as commonfalsepimpernel (Lindernia procumbens), indian toothcup (Rotala indica)and waterwort (Elatine triandra), Cyperaceous weeds such as Sm.fl.umbrella sedge (Cyperus difformis), hardstem bulrush (Scirpur juncoides)and needle spikerush (Eleocharis acicularis) and others such asmonochoria (Monochoria vaginalis) and arrowhead (Sagittaria pygmaea)without producing any phytotoxicity to rice plants on floodingtreatment.

Among the benzothiazolones (I), preferred are those wherein R is C₁ -C₅alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, halo(C₁ -C₄)alkyl, halo(C₃-C₄)alkyl, halo(C₃ -C₄)alkynyl, C₁ -C₂ alkoxy(C₁ -C₂)alkyl, C₁ -C₂alkoxy(C₁ -C₂)alkoxy(C₁ -C₂)alkyl, etc. More preferred are those whereinR is C₂ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl group, halopropynyl,etc. The most preferred are those wherein R is C₂ -C₃ alkyl, C₃ -C₄alkenyl, C₃ -C₄ alkynyl, etc. Typical examples of the preferredcompounds are2-[6-fluoro-3-(1-methylethyl)-2(3H)-benzothiazolon-5-yl]-4,5,6,7-tetrahydro2H-isoindole-1,3-dione,2-[6-fluoro-3-(2-propenyl)-2(3H)benzothiazolon-5-yl]-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione,2-[6-fluoro-3-(2-propynyl)-2(3H)-benzothiazolon-5-yl]-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione,etc.

The benzothiazolones (I) of the invention are obtainable by reacting anamino compound of the formula: ##STR3## whrein R is as defined abovewith 3,4,5,6-tetrahydrophthalic anhydride, usually in a solvent at atemperature of 80° to 200° C. for a period of 1 to 24 hours.

The 3,4,5,6-tetrahydrophthalic anhydride may be used in an amount ofabout 1 to 3 equivalents to the amino compound (II). Examples of solventare aliphatic hydrocarbons (e.g. hexane, heptane, ligroin), aromatichydrocarbons (e.g. benzene, toluene, xylene), ethers (e.g. diisopropylether, dioxane, ethylene glycol dimethyl ether), fatty acids ( e.g.formic acid, acetic acid, propionic acid), water, etc. Their mixturesare also usable.

After completion of the reaction, the reaction mixture is subjected toan ordinary post-treatment such as the addition of water and thecollection of precipitated crystals by filtration. Also, it may besubjected to extraction with an organic solvent and concentration. Ifdesired, any conventional purification procedure such as chromatographyor recrystallization may be adopted.

Typical examples of the benzothiazolones (I) which may be obtainablethrough the above procedure are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                         ##STR4##                      (I)                                            ______________________________________                                        CH.sub.3                                                                      C.sub.2 H.sub.5                                                               n-C.sub.3 H.sub.7                                                             i-C.sub.3 H.sub.7                                                             n-C.sub.4 H.sub.9                                                             i-C.sub.4 H.sub.9                                                             sec-C.sub.4 H.sub.9                                                           t-C.sub.4 H.sub.9                                                             n-C.sub.5 H.sub.11                                                            i-C.sub.5 H.sub.11                                                             ##STR5##                                                                     2-C.sub.5 H.sub.11                                                            3-C.sub.5 H.sub.11                                                             ##STR6##                                                                     neo-C.sub.5 H.sub.11                                                           ##STR7##                                                                     CH.sub.2CHCH.sub.2                                                            CH.sub.3 CHCHCH.sub.2                                                          ##STR8##                                                                     C.sub.6 H.sub.5 CHCHCH.sub.2                                                  CH CCH.sub.2                                                                  CH.sub.3 CCCH.sub.2                                                            ##STR9##                                                                     FCH.sub.2                                                                     ClCH.sub.2                                                                    BrCH.sub.2                                                                    F.sub.2 CH                                                                    Cl.sub.2 CH                                                                   Br.sub.2 CH                                                                   CF.sub.3                                                                      CCl.sub.3                                                                     CBr.sub.3                                                                     FCH.sub.2 CH.sub.2                                                            ClCH.sub.2 CH.sub.2                                                           BrCH.sub.2 CH.sub.2                                                           CF.sub.3 CF.sub.3                                                              ##STR10##                                                                     ##STR11##                                                                     ##STR12##                                                                    ClCH.sub.2 CHCHCH.sub.2                                                       CH.sub.3 (Cl)CCHCH.sub.2                                                      ClCHCHCH.sub.2                                                                 ##STR13##                                                                     ##STR14##                                                                     ##STR15##                                                                    BrCH.sub.2 CHCHCH.sub.2                                                       CH.sub.3 (Br)CCHCH.sub.2                                                      BrCHCHCH.sub.2                                                                ClCCCH.sub.2                                                                  BrCCCH.sub.2                                                                  ICCCH.sub.2                                                                    ##STR16##                                                                     ##STR17##                                                                     ##STR18##                                                                    CH.sub.3 OCH.sub.2                                                            C.sub.2 H.sub.5 OCH.sub.2                                                     CH.sub.3 OCH.sub.2 CH.sub.2                                                   C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2                                            CH.sub.3 OCH.sub.2 OCH.sub.2                                                  CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2                                         C.sub.2 H.sub.5 OCH.sub.2 OCH.sub.2                                           CH.sub.3 OCH.sub.2 OCH.sub.2 CH.sub.2                                         C.sub.2 H.sub.5 OCH.sub.2 OCH.sub.2 CH.sub.2                                  C.sub.2 H.sub.5 OCH.sub.2 CH.sub. 2 OCH.sub.2                                 C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                         NCCH.sub.2                                                                    NCCH.sub.2 CH.sub.2                                                            ##STR19##                                                                     ##STR20##                                                                     ##STR21##                                                                     ##STR22##                                                                     ##STR23##                                                                     ##STR24##                                                                     ##STR25##                                                                     ##STR26##                                                                     ##STR27##                                                                     ##STR28##                                                                     ##STR29##                                                                     ##STR30##                                                                     ##STR31##                                                                     ##STR32##                                                                     ##STR33##                                                                     ##STR34##                                                                     ##STR35##                                                                     ##STR36##                                                                     ##STR37##                                                                     ##STR38##                                                                     ##STR39##                                                                     ##STR40##                                                                     ##STR41##                                                                     ##STR42##                                                                     ##STR43##                                                                     ##STR44##                                                                     ##STR45##                                                                     ##STR46##                                                                     ##STR47##                                                                     ##STR48##                                                                     ##STR49##                                                                     ##STR50##                                                                     ##STR51##                                                                     ##STR52##                                                                     ##STR53##                                                                     ##STR54##                                                                     ##STR55##                                                                     ##STR56##                                                                     ##STR57##                                                                     ##STR58##                                                                     ##STR59##                                                                     ##STR60##                                                                     ##STR61##                                                                     ##STR62##                                                                     ##STR63##                                                                     ##STR64##                                                                     ##STR65##                                                                     ##STR66##                                                                     ##STR67##                                                                     ##STR68##                                                                     ##STR69##                                                                     ##STR70##                                                                     ##STR71##                                                                     ##STR72##                                                                     ##STR73##                                                                     ##STR74##                                                                     ##STR75##                                                                     ##STR76##                                                                     ##STR77##                                                                     ##STR78##                                                                     ##STR79##                                                                     ##STR80##                                                                     ##STR81##                                                                     ##STR82##                                                                     ##STR83##                                                                     ##STR84##                                                                     ##STR85##                                                                     ##STR86##                                                                     ##STR87##                                                                     ##STR88##                                                                     ##STR89##                                                                     ##STR90##                                                                     ##STR91##                                                                     ##STR92##                                                                     ##STR93##                                                                     ##STR94##                                                                     ##STR95##                                                                     ##STR96##                                                                     ##STR97##                                                                     ##STR98##                                                                     ##STR99##                                                                     ##STR100##                                                                    ##STR101##                                                                    ##STR102##                                                                    ##STR103##                                                                    ##STR104##                                                                    ##STR105##                                                                    ##STR106##                                                                    ##STR107##                                                                    ##STR108##                                                                    ##STR109##                                                                    ##STR110##                                                                    ##STR111##                                                                    ##STR112##                                                                    ##STR113##                                                                    ##STR114##                                                                   ______________________________________                                    

Practical and presently preferred embodiments for production of thebenzothiazolones (I) are illustratively shown in the following Examples.

EXAMPLE 1

5-Amino-6-fluoro-3-(2-propynyl)-2(3H)-benzothiazolone (0.43 g) and3,4,5,6-tetrahydrophthalic anhydride (0.32 g) were suspended in aceticacid (5 ml), and the resultant suspension was heated under reflux for 5hours. After being allowed to cool, water was added thereto, and theresultant mixture was extracted with ethyl acetate. The extract waswashed with water and an aqueous sodium bicarbonate solution, dried andconcentrated. The residue was purified by silica gel thin layerchromatography with a mixture of ethyl acetate and hexane (1:4) to give2-[6-fluoro-3-(2-propynyl)-2(3H)-benzothiazolon-5-yl]-4,5,6,7-tetrahydro-2H-isoindole-1,3-dione(0.13 g). m.p., 193°-195° C. Recrystallization from 2-propanol gave thepurified product. m.p., 198°-199° C.

IR (KBr, CHCl₃) cm⁻¹ : 3300, 3020, 1720, 1685, 1490, 1385, 1215, 760,665.

¹ HNMR (CHCl₃, δ): 1.5-2.0 (4H, br.), 2.1-2.6 (5H, br.), 4.61 (2H, d,J=2.6 Hz), 7.06 (1H, d, J=6.0 Hz), 7.27 (1H, d, J=9.0 Hz).

EXAMPLE 2

5-Amino-3-ethoxycarbonylmethyl-6-fluoro-2(3H)benzothiazolone (140 mg)and 3,4,5,6-tetrahydrophthalic anhydride (90 mg) were suspended inacetic acid (3 ml), and the resultant suspension was heated under refluxfor 5 hours. After being allowed to cool, water was added thereto, andthe resultant mixture was extracted with ethyl acetate. The extract wswashed with water and sodium bicarbonte solution, dried andconcentrated. The residue was purified by silica gel thin layerchromatography with a mixture of ethyl acetate and hexane (1:2) to give2-[3-ethoxycarbonylmethyl-6-fluoro-2(3H)-benzothiazolon-5-yl]4,5,6,7-tetrahydro-2H-isoindole-1,3-dione(40 mg). m.p., 155.5°-156.5° C.

In the same manner as above, the benzothiazolones (I) as shown in Table2 were obtained.

                  TABLE 2                                                         ______________________________________                                         ##STR115##                    (I)                                            Com-                                                                          pound                                                                         No.   R                    Physical property                                  ______________________________________                                        1     H                    m.p., 247.5° C.                             2     CH.sub.3             m.p., 189.5-190.5° C.                       3     C.sub.2 H.sub.5      m.p., 117-119° C.                           4     n-C.sub.3 H.sub.7    m.p., 158-159° C.                           5     i-C.sub.3 H.sub.7    n.sub.D.sup.24.4 1.5633                            6     n-C.sub.4 H.sub.9    m.p., 183-184° C.                           7     i-C.sub.4 H.sub.9    m.p., 182.5-184.0° C.                       8     sec-C.sub.4 H.sub.9  m.p., 180.5-181.0° C.                       9     n-C.sub.5 H.sub.11   n.sub.D.sup.22.0 1.5691                            10    i-C.sub.5 H.sub.11   n.sub.D.sup.21.7 1.5640                            11    3-C.sub.5 H.sub.11   m.p., 168.5-170.0° C.                       12    CH.sub.2CHCH.sub.2   m.p., 136.5-138.5° C.                       13    CH.sub.3 CHCHCH.sub.2                                                                              m.p., 152.5-154.0° C.                       14                                                                                   ##STR116##          m.p., 85-86° C.                             15    C.sub.6 H.sub.5 CHCHCH.sub.2                                                                       m.p., 62.5-64.0° C.                         16    CHCCH.sub.2          m.p., 193-195° C.                           17                                                                                   ##STR117##          m.p., 110-111                                      18    FCH.sub.2 CH.sub.2   n.sub.D.sup.25.2 1.5763                            19    ClCH.sub.2 CH.sub.2  m.p., 180.5° C.                             20    BrCH.sub.2 CH.sub.2  m.p., 195° C.                               21                                                                                   ##STR118##          m.p., 59-60° C.                             22                                                                                   ##STR119##          m.p., 191-192° C.                           23                                                                                   ##STR120##          m.p., 151-153° C.                           24    ClCH.sub.2 CHCHCH.sub.2                                                                            n.sub.D.sup.21.0 1.5824                            25    CH.sub.3 (Cl)CCHCH.sub.2                                                                           n.sub.D.sup.18.5 1.5870                            26    ClCHCHCH.sub.2       n.sub.D.sup.20.0 1.5844                            27    BrCCCH.sub.2         m.p., 192.5-194.0° C.                       28    CH.sub.3 OCH.sub.2   m.p., 155-156° C.                           29    C.sub.2 H.sub.5 OCH.sub.2                                                                          m.p., 194-195° C.                           30    CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2                                                              m.p., 123-125° C.                           31    NCCH.sub.2           m.p., 195-196° C.                           32    NCCH.sub.2 CH.sub.2  m.p., 192° C.                               33                                                                                   ##STR121##          m.p., 289.4° C.                             34                                                                                   ##STR122##          m.p., 222.0-223.0° C.                       35                                                                                   ##STR123##          m.p., 155.5-156.5° C.                       36                                                                                   ##STR124##          n.sub.D.sup.27.2 1.5520                            37                                                                                   ##STR125##          m.p., 164.0-165.0° C.                       38                                                                                   ##STR126##          m.p., 174.9° C.                             39                                                                                   ##STR127##          n.sub.D.sup.29.0 1.5616                            40                                                                                   ##STR128##          n.sub.D.sup.29.0 1.5800                            41                                                                                   ##STR129##          m.p., 200.5-202.0° C.                       42                                                                                   ##STR130##          n.sub.D.sup.29.0 1.5531                            43                                                                                   ##STR131##          n.sub.D.sup.27.7 1.5508                            44                                                                                   ##STR132##          m.p., 80-82° C.                             45                                                                                   ##STR133##          n.sub.D.sup.29.0 1.5752                            46                                                                                   ##STR134##          n.sub.D.sup.28.5 1.5383                            47                                                                                   ##STR135##          n.sub.D.sup.28.5 1.5464                            ______________________________________                                    

The amino compound (II) as the starting material in the process of thisinvention may be produced according to the following scheme: ##STR136##wherein R is as defined above and R¹ has the same meaning as R expectcarboxyethyl, 2-(C₁ -C₅)alkoxycarbonylethyl, 2-halo(C₁-C₅)alkoxycarbonylethyl, 2-(C₁ -C₂)alkoxy(C₁ -C₂)alkoxycarbonylethyl,2-(C₁ -C₅)alkoxycarbonyl(C₁ -C₂)alkoxycarbonylethyl, 2-cyclo(C₃-C₆)alkoxycarbonylethyl, 2-(C₁ -C₅)alkylaminocarbonylethyl and 2-di(C₁-C₅)alkylaminocarbonylethyl, R² has the same meaning as R¹ except##STR137## R³ and R⁴ are each C₁ -C₄ alkyl but the total number ofcarbon atoms in R³ and R⁴ does not exceed 4, X is chlorine, bromine,iodine, methanesulfonyloxy or p-toluenesulfonyloxy and Y is hydroxyl, C₁-C₅ alkoxy, halo(C₁ -C₅)alkoxy, C₁ -C₂ alkoxy(C₁ -C₂)alkoxy, C₁ -C₅alkoxycarbonyl(C₁ -C₂)alkoxy, cyclo(C₃ -C₆)alkoxy, C₁ -C₅ alkylamino ordi(C₁ -C₅)alkylmaino.

Each reaction as set forth above will be hereinafter explained indetail.

(1) Production of the compound (II) from the compound (III), (IV) or(VIII) (Procedure 1):

The compound (II) is obtainable by reacting the compound (III), (IV) or(VIII) with a reducing agent (e.g. iron powder) at a temperature of 60°to 120° C. for a period of 10 minutes to 12 hours. Preferably, thereaction is effected in a solvent such as acetic acid and ethyl acetate.In the reaction, the reducing agent is used in an amount of 3 to 30equivalents, preferably of 5 to 20 equivalents, to one equivalent of thecompound (III), (IV) or (VIII).

After completion of the reaction, the residue is collected byfiltration, and the filtrate is washed with an organic solvent. Theextract is washed with water and a sodium bicarbonate solution andsubjected to concentration to obtain the compound (II). If necessary,any purification method such as recrystallization or chromatography maybe applied to the product.

(2) Production of the compound (III) from the compound (VIII) (Procedure2):

The compound (III) is obtainable by reacting the compound (VIII) withthe compound (V) in the presence of a base (e.g. sodium hybride,potassium carbonate, sodium hydroxide, potassium hydroxide) at atemperature of 0° to 120° C. for a period of 30 minutes to 24 hours in asolvent such as an aromatic hydrocarbon (e.g. toluene, benzene), anamide (e.g. N,N-dimethylformamide), a sulfur compound (e.g.dimethylsulfoxide), a nitrile (e.g. acetonitrile) or water, or theirmixture. In the reaction, the compound (V) and the base are respectivelyused in an amount of 1 to 1.5 equivalents to one equivalent of compound(VIII). The recovery of the compound (III) can be accomplished by addingwater to the reaction mixture, extracting the resultant mixture with anorganic solvent and concentrating the extract. When desired, anypurification procedure such as recrystallization or chromatography maybe adopted.

(3) Production of the compound (IV) from the compound (VIII) (Procedure3):

The compound (IV) can be obtained by reacting the compound (VIII) withthe compound (VI) in the presence of a base (e.g. benzyltrimethylammonium hydroxide) at a temperature of 50° to 100° C. for aperiod of 30 minutes to 24 hours, ordinarily in a solvent such asaromatic hydrocarbon (e.g. toluene, benzene), an amide (e.g.N,N-dimethylformamide), a sulfur compound (e.g. dimethylsulfoxide), anitrile (e.g. acetonitrie) or water, or a mixture thereof. In thereaction, the compound (VI) and the base are respectively used in anamount of 1.0 equivalent to excess and 1.0 to 3 equivalents to oneequivalent of the compound (VIII). The recovery of the compound (IV) canbe accomplished by adding water to the reaction mixture, extracting theresultant mixture with an organic solvent and concentrating the extract.When desired, any purifiction procedure such as recrystallization orchromatography may be adopted.

(4) Production of the compound (VIII) (Procedure 4):

The compound (VIII) is obtained by reacting the compound (X) with anitrating agent (e.g. a mixture of sulfuric acid and nitric acid) at atemperature -10° to 10° C. instantaneously or within 5 hours. In thereaction, sulfuric acid and nitric acid are used respectively in anamount of 1 equivalent to excess and 1 to 1.2 equivalents to oneequivalent of the compound (X). After completion of the reaction, theresultant mixture is subjected to conventional post-treatment. Forinstance, it is poured into ice-water, and precipitated crystals arecollected by filtration and washed with water. When desired, theresulting product may be further purified by recrystallization orchromatography.

The starting compound (X) may also be prepared according to the methodas described in G. Mazzone and G. Pappalaro: Farmaco, Ed., Sc., 32 (5),348 (1977).

(5) Production of the compound (III) (Procedure 5):

The compound (III) may be obtainable by reacting the compound (VII) witha nitrating agent (e.g. a mixture of sulfuric acid and nitric acid) at atemperature of -10° to 10° C. instantaneously or within 5 hours. In thereaction, sulfuric acid and nitric acid are used respectively in anamount of 1 equivalent to excess and 1 to 1.2 equivalents to oneequivalent of the compound (VII). After completion of the reaction, theresultant mixture is subjected to a conventional post-treatment. Forinstance, it is poured into ice-water, and precipitated crystals arecollected by filtration and washed with water. When desired, theresulting product may be further purified by recrystallization orchromatography.

(6) Production of the compound (VII):

The compound (VII) can be prepared from the compound (IX) by the methodas described in Japanese Patent Publication (unexamined) Nos.123480/1985 and 166673/1985.

The intermediates, i.e. the compounds (II), (III), (IV) and (VIII), arenovel and can be represented by the general formula: ##STR138## whereinR is as defined above and A is amino or nitro.

Typical examples for production of the intermediates are illustrativelyshown in the following examples.

EXAMPLE 3 (Procedure 1)

Electrolytic iron powder (0.77 g) was suspended in 5% acetic acid (1.5ml), and the suspension was heated to 80° C. A solution of3-allyl-6-fluoro-5-nitro-2(3H)-benzothiazolone (0.70 g) in acetic acid(2.8 ml) and ethyl acetate (2.8 ml) was added thereto. The resultantmixture was heated under reflux at a temperature of 60° to 80° C. for 3hours. After being allowed to cool, water and ethyl acetate were addedthereto, the precipitate was collected by filtration, and the filtratewas extracted with ethyl acetate. The extract was washed with water andsodium bicarbonate solution, dried and concentrated to give 0.60 g of5-amino-3-allyl-6-fluoro-2(3H)-benzothiazolone. n_(D) ²⁶.0 1.6236.

EXAMPLE 4 (Procedure 1)

Electrolytic iron powder (0.29 g) was suspended in 5% acetic acid (2ml), and a solution of3-ethoxycarbonylmethyl-6-fluoro-5-nitro-2(3H)-benzothiazolone (0.31 g)in acetic acid (1 ml) and ethyl acetate (1 ml) was dropwise addedthereto while heating. The resultant mixture was heated under reflux for3 hours. The reaction mixture was subjected to filtration with celite,and the filtrate was extracted with ethyl acetate. The extract waswashed with water and sodium bicarbonate solution, dried andconcentrated to give 0.20 g of5-amino-3-ethoxycarbonylmethyl-6-fluoro-2(3H)-benzothiazolone. m.p.,172.5°-173.5° C.

In the same manner as above, the compounds (II) as shown in Table 3 wereobtained.

                  TABLE 3                                                         ______________________________________                                         ##STR139##                   (II)                                            R                     Physical property                                       ______________________________________                                        CH.sub.3              m.p., 188-189° C.                                C.sub.2 H.sub.5       m.p., 117-119° C.                                n-C.sub.3 H.sub.7     n.sub.D.sup.25.3 1.6000                                 i-C.sub.3 H.sub.7     n.sub.D.sup.24.4 1.6056                                 n-C.sub.4 H.sub.9     n.sub.D.sup.22.0 1.5910                                 i-C.sub.4 H.sub.9     m.p., 113-114° C.                                sec-C.sub.4 H.sub.9   n.sub.D.sup.23.5 1.5933                                 n-C.sub.5 H.sub.11    n.sub.D.sup.22.0 1.5691                                 i-C.sub.5 H.sub.11    n.sub.D.sup.21.7 1.5824                                 3-C.sub.5 H.sub.11    m.p., 102° C.                                    CH.sub.2CHCH.sub.2    n.sub.D.sup.26.0 1.6236                                  ##STR140##           m.p., 96-97° C.                                  C.sub.6 H.sub.5 CHCHCH.sub.2                                                                        m.p., 104.5-105.0° C.                            CHCCH.sub.2           m.p., 124-126° C.                                 ##STR141##           m.p., 128.5-129.5° C.                            FCH.sub.2 CH.sub.2    m.p., 133-134° C.                                ClCH.sub.2 CH.sub.2   m.p., 126.5-128.0° C.                            BrCH.sub.2 CH.sub.2   m.p., 113-114° C.                                 ##STR142##           m.p., 140-142° C.                                 ##STR143##           m.p., 142.5-143.5° C.                             ##STR144##           m.p., 136-137° C.                                ClCH.sub.2 CHCHCH.sub.2                                                                             m.p., 237-239° C.                                 ##STR145##           m.p., 103-104° C.                                 ##STR146##           m.p., 90.5-91.0° C.                               ##STR147##           m.p., 139-140° C.                                 ##STR148##           n.sub.D.sup.21.0 1.6323                                 BrCCCH.sub.2          m.p., 174.5-175.0° C.                            CH.sub.3 OCH.sub.2    m.p., 112-113° C.                                C.sub.2 H.sub.5 OCH.sub.2                                                                           m.p., 77-78° C.                                  CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2                                                               m.p., 99.5-100.5° C.                             NCCH.sub.2            m.p., 153.5-154.5° C.                            NCCH.sub.2 CH.sub.2   m.p., 175° C.                                     ##STR149##           resinous                                                 ##STR150##           m.p., 155.5-156.5° C.                             ##STR151##           m.p., 172.5-173.5° C.                             ##STR152##           n.sub.D.sup.27.7 1.5651                                  ##STR153##           m.p., 120.0-125.0° C.                             ##STR154##           m.p., 124.1° C.                                   ##STR155##           m.p., 79.1° C.                                    ##STR156##           m.p., 155-157° C.                                 ##STR157##           visous solid                                             ##STR158##           n.sub.D.sup.27.7 1.5642                                  ##STR159##           n.sub.D.sup.28.0 1.5744                                  ##STR160##           n.sub.D.sup.29.0 1.5655                                  ##STR161##           resinous                                                 ##STR162##           n.sub.D.sup.28.5 1.5556                                 ______________________________________                                    

EXAMPLE 5 (Procedure 2)

60% Oily sodium hydride (0.21 g) was suspended in N,N-dimethylformamide(7 ml), and the resultant suspension was cooled to 0° C.6-Fluoro-5-nitro-2(3H)-benzothiazolone (1.0 g) was added thereto at 0°to 5° C., and the mixture was stirred for 30 minutes. Allyl bromide(0.62 g) was added to the reaction mixture, and the temperature wasgradually elevated to a temperature of 50° to 60° C. The mixture wasallowed to react at that temperature for 3 hours. Water was added to themixture, which was extracted with ethyl acetate. The extract was washedwith water, dried and concentrated. The residue was purified by silicagel thin layer chromatography with a mixture of ethyl acetate andtoluene (1:9) to give 0.70 g of3-allyl-7-fluoro-6-nitro-2(3H)-benzothiazolone. m.p., 112.5°-113.5° C.

EXAMPLE 6 (Procedure 2)

50% Oily sodium hydride (0.21 g) was suspended in N,N-dimethylformamide(5 ml), and the resultant suspension was cooled to 0° C.6-Fluoro-5-nitro-2(3H)-benzothiazolone (1.0 g) was portionwise addedthereto at 0° C., and the mixture was stirred at the same temperaturefor 30 minutes. Ethyl bromoacetate (0.86 g) was added to the reactionmixture at 0° C., and the temperature was gradually elevated to atemperature of 50° to 60° C., followed by stirring at that temperaturefor 3 hours. Water was added to the mixture, which was extracted withethyl acetate. The extract was washed with water, dried andconcentrated. The residue was purified by silica gel thin layerchromatography with a mixture of ethyl acetate and toluene (1:9) to give0.35 g of 3-ethoxycarbonylmethyl-6-fluoro-5-nitro-2(3H)-benzothiazolone,m.p., 139.0°-140.0° C.

EXAMPLE 7 (Procedure 3)

A mixture of 6-fluoro-5-nitnro-2(3H)-benzothiazolone (1.0 g), methylacrylate (5 ml) and a 40% methanolic solution of benzyltrimethylammoniumhydroxide (1.95 g) was heated under reflux for 2 hours, followed bycooling. Water was added to the reaction mixture, which was extractedwith ethyl acetate. The extract was washed with water, dried andconcentrated to give 1.12 g of6-fluoro-3-(2-methoxycarbonyl)ethyl-5-nitro-2(3H)-benzothiazolone, m.p.,224.3° C.

EXAMPLE 8 (Procedure 5)

6-Fluoro-3-(1-methylethyl)-2(3H)-benzothiazolone (299 g) was dissolvedin conc. sulfuric acid (8750 g), and the resultant mixture was cooled toa temperature of -5° to 0° C. 98% fuming nitric acid (d=1.52) (94.68 g)was dropwise added thereto while keeping the temperature at 0° C.,followed by stirring for 1 hour. The reaction mixture was poured intoice-water (16 kg), and the precipitated crystals were collected byfiltration. Crystals were washed with water and dried to give 325 g of6-fluoro-3-(1-methylethyl)-5-nitro-2(3H)-benzothiazolone. m.p.,153°-153.5° C.

In the same manner as above, the compounds (III) or (IV) as shown inTable 4 were obtained.

                  TABLE 4                                                         ______________________________________                                         ##STR163##                                                                   R                    Physical property                                        ______________________________________                                        CH.sub.3             m.p., 148-149° C.                                 C.sub.2 H.sub.5      m.p., 128-128.5° C.                               n-C.sub.3 H.sub.7    m.p., 71-73° C.                                   i-C.sub.3 H.sub.7    m.p., 153-153.5° C.                               n-C.sub.4 H.sub.9    m.p., 83-84° C.                                   i-C.sub.4 H.sub.9    m.p., 101.5-103.0° C.                             sec-C.sub.4 H.sub.9  m.p., 87-88° C.                                   n-C.sub.5 H.sub.11   m.p., 68.5-69.5° C.                               i-C.sub.5 H.sub.11   n.sub.D.sup.22.0 1.5900                                  3-C.sub.5 H.sub.11   m.p., 110-111° C.                                 CH.sub.2CHCH.sub.2   m.p., 112.5-113.5° C.                             CH.sub.3 CHCHCH.sub.2                                                                              m.p., 84-85° C.                                    ##STR164##          m.p., 83-84° C.                                   C.sub.6 H.sub.5 CHCHCH.sub.2                                                                       m.p., 106-107° C.                                 CHCCH.sub.2          m.p., 123.5- 124.5° C.                             ##STR165##          m.p., 183.5-184.5° C.                             FCH.sub.2 CH.sub.2   m.p., 136-137° C.                                 ClCH.sub.2 CH.sub.2  m.p., 125-126° C.                                 BrCH.sub.2 CH.sub.2  m.p., 128.5-129.5° C.                              ##STR166##          n.sub.D.sup.22.5 1.6224                                   ##STR167##          m.p., 133° C.                                      ##STR168##          n.sub.D.sup.22.2 1.6340                                  ClCH.sub.2 CHCHCH.sub.2                                                                            n.sub.D.sup.21.7 1.6217                                  CH.sub.3 (Cl)CCHCH.sub.2                                                                           n.sub.D.sup.18.5 1.6153                                  ClCHCHCH.sub.2       n.sub.D.sup.18.5 1.6287                                  BrCCCH.sub.2         m.p., 134.5-136.0° C.                             CH.sub.3 OCH.sub.2   m.p., 125-126° C.                                 C.sub.2 H.sub.5 OCH.sub.2                                                                          m.p., 114-115° C.                                 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2                                                              m.p., 78- 80° C.                                  NCCH.sub.2           m.p., 146.5-147.5° C.                             NCCH.sub.2 CH.sub.2  m.p., 174-176° C.                                  ##STR169##          m.p., 264.2° C.                                    ##STR170##          m.p., 163.5-165.0° C.                              ##STR171##          m.p., 139.0-140.0° C.                              ##STR172##          m.p., 75.0-76.0° C.                                ##STR173##          m.p., 124.5-125.5° C.                              ##STR174##          m.p., 224.3° C.                                    ##STR175##          m.p., 79.1° C.                                     ##STR176##          m.p., 118.0-120.0° C.                              ##STR177##          m.p., 90.5-91.5° C.                                ##STR178##          m.p., 110.0-112.0° C.                              ##STR179##          m.p., 121.5-123.0° C.                              ##STR180##          n.sub.D.sup.29.0 1.5914                                   ##STR181##          n.sub.D.sup.29.0 1.5743                                   ##STR182##          n.sub.D.sup.28.5 1.5445                                  ______________________________________                                    

EXAMPLE 9 (Procedure 4)

6-Fluoro-2(3H)-benzothiazolone (47.58 g) was dissolved in 100% sulfuricacid (760 ml), and the resultant mixture was cooled to 0° to 5° C. 98%fuming nitric acid (d=1.52) (18.79 g) was gradually added thereto at atemperature of 0° to 5° C., followed by stirring at the same temperaturefor 60 minutes. The reaction mixture was poured into ice-water. Theprecipitated crystals were collected by filtration, washed with waterand air-dried to give 48.48 g of 6-fluoro-5-nitro-2(3H)-benzothiazoloneas pale brown crystals. m.p., 180°-182° C.

In the practical use of the benzothiazolones (I), they may be applied inconventional preparation forms such as emulsifiable concentrates,wettable powders, suspensions and granules in combination withconventional solid or liquid carriers or diluents as well as surfaceactive agents or auxiliary agents. The content of the benzothiazolones(I) as the active ingredient in such preparation forms is usually withina range of 0.05 to 90% by weight, preferably of 0.1 to 80% by weight.Examples of the solid carrier or diluent are fine powders or granules ofkaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite,talc, diatomaceous earth, calcite, walnut powders, urea, ammoniumsulfate and synthetic hydrous silicate, etc. As the liquid carrier ordiluent, there may be exemplified aromatic hydrocarbons (e.g. xylene,methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol,cellosolve), ketones (e.g. acetone, cyclohexanone, isophorone), soybeanoil, cotton seed oil, dimethylsulfoxide, N,N-dimethylformamide,acetonitrile, water, etc.

The surface active agent used for emulsification, dispersion orspreading may be any of the anionic and non-ionic type of agents.Examples of the surface active agent include alkylsulfates,alkylarylsulfonates, dialkylsulfosuccinates, phosphates ofpolyoxyethylenealkylaryl ethers, polyoxyethylene alkyl ethers,polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene blockcopolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fattyacid esters, etc. Examples of the auxiliary agents includeligninsulfonates, sodium alginate, polyvinyl alcohol, gum arabic, CMC(carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.

Practical embodiments of the herbicidal composition according to theinvention are illustratively shown in the following examples whereinparts are by weight. The compound number of the active ingredientcorresponds to those in Table 2.

FORMULATION EXAMPLE 1

Fifty parts of Compound Nos. 2, 4, 34 or 35, 3 parts of calciumligninsulfonate, 2 parts of sodium laurylsulfate and 45 parts ofsynthetic hydrous silicate are mixed well while being powdered to obtaina wettable powder.

FORMULATION EXAMPLE 2

Five parts of Compound Nos. 5, 14 parts of polyoxyethylenestyrylphenylether, 6 parts of calcium dodecylbenzenesulfonate, 30 parts of xyleneand 45 parts of cyclohexanone are mixed well to obtain an emulsifiableconcentrate.

FORMULATION EXAMPLE 3

Ten parts of Compound No. 37 or 43, 14 parts ofpolyoxyethylenestyrylphenyl ether, 6 parts of calciumdodecylbenzenesulfonate, 25 parts of xylene and 45 parts ofcyclohexanone are mixed well to obtain an emulsifiable concentrate.

FORMULATION EXAMPLE 4

Two parts of Compound Nos. 3, 12, 16, 34 or 44, 1 part of synthetichydrous silicate, 2 parts of calcium ligninsulfonate, 30 parts ofbentonite and 65 parts of kaolin clay are mixed well while beingpowdered. The mixture is then kneaded with water, granulated and driedto obtain granules.

FORMULATION EXAMPLE 5

Twenty-five parts of Compound Nos. 4, 16, 29, 37 or 41 is mixed with 3parts of polyoxyethylene sorbitan monooleate, 3 parts of carboxymethylcellulose and 69 parts of water and pulverized until the particle sizeof the mixture becomes less than 5 microns to obtain a suspension.

FORMULATION EXAMPLE 6

Five parts of Compound Nos. 2, 3, 4, 5, 12, 16, 17, 28, 29, 31, 36 or38, 14 parts of polyoxyethylenestyrylphenyl ether, 6 parts of calciumdodecylbenzenesulfonate, 30 parts of xylene and 45 parts ofN,N-dimethylformamide are mixed well to obtain an emulsifiableconcentrate.

The benzothiazolones (I) thus formulated in any suitable formulationform are useful for the pre-emergence or post-emergence control ofundesired weeds by soil or foliar treatment as well as flood fallowingtreatment. These treatments include application to the soil surfaceprior to or after the transplanting or the incorporation into the soil.The foliar treatment may be effected by spraying the herbicidalcomposition containing the benzothiazolones (I) over the top of theplants. It may also be applied directly to the weeds if care is taken tokeep the chemical off the crop foliage.

The benzothiazolones (I) of the invention may be used together withother herbicides to improve their activity as herbicides, and in somecases, a synergistic effect can be expected. Further, they may beapplied in combination with insecticides, acaricides, nematocides,fungicides, plant growth regulators, fertilizers, soil improvers, etc.

Furthermore, the benzothiazolones (I) can be used as herbicidesapplicable to agricultural plowed fields as well as paddy fields. Theyare also useful as herbicides to be employed for orchards, pasturelands, lawns, forests, non-agricultural fields, etc.

The dosage rate of the benzothiazolones (I) may vary depending onprevailing weather conditions, formulation used, prevailing season, modeof application, soil involved, crop and weed species, etc. Generally,however, the dosage rate is from 0.02 to 100 grams, preferably from 0.05to 50 grams, of the active ingredient per are. The herbicidalcomposition of the invention formulated in the form of an emulsifiableconcentrate, a wettable powder or a suspension may ordinarily beemployed by diluting it with water at a volume of 1 to 10 liters perare, if necessary, with addition of an auxiliary agent such as aspreading agent. Examples of the spreading agent include, in addition tothe surface active agents as noted above, polyoxyethylene resin acid(ester), ligninsulfonate, abietylenic acid, salt,dinaphthylmethanedisulfonate. paraffin, etc. The composition formulatedin the form of granules may be normally applied as such withoutdilution.

The biological data of the benzothiazolones (I) as herbicides will beillustratively shown in the following Examples wherein the phytotoxicityto crop plants and the herbicidal activity on weeds were observedvisually as to the degree of germination as well as the growthinhibition and rated with an index 0, 1, 2, 3, 4 or 5, in which thenumeral "0" indicates that no material difference is seen in comparisonwith the untreated plant and the numeral "5" indicates the completeinhibition or death of the test plants.

The compounds shown in Table 5 below were used for comparison.

                  TABLE 5                                                         ______________________________________                                        Com-                                                                          pound                                                                         No.   Chemical structure    Remarks                                           ______________________________________                                               ##STR183##           Commercially available herbi- cide                                            "benazolin"                                       B                                                                                    ##STR184##           Commercially available herbi- cide                ______________________________________                                                                    "cyanazin"                                    

Test Example 1

Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filledwith upland field soil, and the seeds of Japanese millet, oats, tallmorningglory and velvetleaf were sowed therein and covered with soil. Adesignated amount of the test compound formulated in an emulsifiableconcentrate according to Formulation Example 2, 3 or 6 was diluted withwater, and the dilution was sprayed onto the soil surface by means of asmall hand sprayer at a spray volume of 10 liters per are. The testplants were further grown in a greenhouse for 20 days, and theherbicidal activity was examined. The results are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                                     Herbicidal activity                                                                               Tall                                         Compound   Dosage  Japanese      morning-                                                                             Velvet-                               No.        (g/are) millet   Oats glory  leaf                                  ______________________________________                                        2          20      5        5    5      5                                     3          20      5        5    5      5                                     4          20      5        5    5      5                                     5          20      5        5    5      5                                     6          20      5        5    5      5                                     7          20      4        --   5      5                                     8          20      5        5    5      5                                     9          20      4        4    5      5                                     10         20      4        4    4      5                                     12         20      5        5    5      5                                     13         20      4        4    4      5                                     14         20      4        4    5      5                                     16         20      5        5    5      5                                     17         20      5        5    5      5                                     18         20      5        5    5      5                                     19         20      5        5    5      5                                     20         20      5        4    4      5                                     22         20      5        --   4      5                                     25         20      --       --   5      5                                     26         20      5        4    5      5                                     27         20      5        5    5      5                                     28         20      5        5    5      5                                     29         20      5        5    5      5                                     30         20      5        5    5      5                                     31         20      5        5    5      5                                     32         20      5        5    5      5                                     35         20      --       --   5      5                                     37         20      5        --   5      5                                     38         20      --       --   4      5                                     39         20      --       --   5      5                                     41         20      --       --   5      5                                     44         20      --       --   5      5                                     45         20      --       --   5      5                                     47         20      5        --   5      5                                     ______________________________________                                    

Test Example 2

Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filledwith upland field soil, and the seeds of Japanese millet, radish andvelvetleaf were sowed therein and cultivated in a greenhouse for 10days. A designated amount of the test compound formulated in anemulsifiable concentrate according to Formulation Example 2, 3 or 6 wasdiluted with water containing a spreading agent, and the dilution wassprayed over the foliage of the test plants by means of a small handsprayer at a spray volume of 10 liters per are. The test plants werefurther grown in the greenhouse for 20 days, and the herbicidal activitywas examined. The results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        Compound   Dosage  Herbicidal activity                                        No.        (g/are) Japanese millet                                                                           Radish                                                                              Velvetleaf                               ______________________________________                                        1          20      5           5     5                                        2          20      5           5     5                                        3          20      5           5     5                                        4          20      5           5     5                                        5          20      4           5     5                                        6          20      5           5     5                                        7          20      5           5     5                                        8          20      5           5     5                                        9          20      5           5     5                                        10         20      5           5     5                                        11         20      5           5     5                                        12         20      5           5     5                                        13         20      5           5     5                                        15         20      5           5     5                                        16         20      5           5     5                                        19         20      5           5     5                                        20         20      5           5     5                                        21         20      5           5     5                                        22         20      5           5     5                                        23         20      5           5     5                                        24         20      5           5     5                                        25         20      5           5     5                                        26         20      5           5     5                                        27         20      5           5     5                                        28         20      5           5     5                                        29         20      5           5     5                                        30         20      5           5     5                                        31         20      5           5     5                                        32         20      5           5     5                                        33         20      5           5     5                                        34         20      5           5     5                                        35         20      5           5     5                                        36         20      5           5     5                                        37         20      5           5     5                                        38         20      4           5     5                                        39         20      4           5     5                                        40         20      5           5     5                                        41         20      5           5     5                                        42         20      5           5     5                                        43         20      5           5     5                                        44         20      5           5     5                                        45         20      5           5     5                                        46         20      5           5     5                                        47         20      5           5     5                                        ______________________________________                                    

Test Example 3

Cylindrical plastic pots (diameter, 8 cm,; height, 12 cm) were filledwith paddy field soil, and the seeds of barnyardgras (Echinochloaoryzicola), and broad-leaved weeds (i.e. common falsepimpernel, indiantoothcup, waterwort) were sowed in 1 to 2 cm depth. Water was pouredtherein to make a flooded condition. Buds of arrowhead were sowed in 1to 2 cm depth, and rice seedlings of the 2.5-leaf stage weretransplanted therein, and the test plants were grown in a greenhouse.Six days (at that time weeds began to germinate) thereafter, adesignated amount of the test compound formulated in an emulsifiableconcentrate according to Formulation Example 2, 3 or 6 and diluted withwater (5 ml) was applied to the pots by perfusion. The test plants weregrown for an additional 20 days in the greenhouse, and the herbicidalactivity was examined. The results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                                  Herbicidal activity                                                 Compound                                                                              Dosage  Rice   Barnyard-                                                                             Broad-leaved                                                                           Arrow-                                No.     (g/are) plant  grass   weed     head                                  ______________________________________                                        3       2.5     --     5       5        5                                             0.63    0      5       5        5                                     5       2.5     --     5       5        5                                             0.63    --     5       5        5                                     12      2.5     --     5       5        5                                             0.63    0      5       5        5                                     16      0.63    --     5       5        5                                     27      2.5     --     5       5        4                                             0.63    1      4       5        --                                    37      2.5     1      5       5        5                                             0.63    1      5       5        --                                    38      2.5     1      4       4        5                                     39      2.5     1      5       5        5                                     44      2.5     0      4       4        5                                     A       2.5     0      1       3        1                                             0.63    0      0       1        0                                     ______________________________________                                    

Test Example 4

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of soybean, peanut, cotton, corn, tall morningglory, velvetleaf,redweed pigweed, black nightshade, common lambsquarters, sicklepod,barnyardgrass (Echinochloa crus-galli), johnsongrass and green foxtailwere sowed therein to 1 to 2 cm depth. A designated amount of the testcompound formulated in an emulsifiable concentrate according toFormulation Example 2, 3 or 6 was diluted with water, and the dilutionwas sprayed onto the soil surface by means of a small hand sprayer at aspray volume of 10 liters per are. The test plants were further grown ina greenhouse for 20 days, and the herbicidal activity was examined. Theresults are shown in Table 9.

                                      TABLE 9                                     __________________________________________________________________________            Herbicidal activity                                                   Com-                  Tall      Black    Common   Barn-                                                                             Green                   pound                                                                             Dosage                                                                            Soy-          morning-                                                                           Velvet-                                                                            night-                                                                            Redroot                                                                            lambs-                                                                             Sickle-                                                                           yard-                                                                             fox-                                                                              Johnson-            No. (g/are)                                                                           bean                                                                             Peanut                                                                            Cotton                                                                            Corn                                                                             glory                                                                              leaf shade                                                                             pigweed                                                                            quarters                                                                           pod grass                                                                             tail                                                                              grass               __________________________________________________________________________    2   2.5 0  0   1   1  5    5    4   5    5    4   4   5   5                   3   2.5 3  --  4   2  5    5    5   5    5    --  5   5   5                       1.25                                                                              1  0   2   0  --   5    5   5    4    --  3   4   3                   4   2.5 1  0   1   0  5    5    5   5    5    5   4   5   4                   5   2.5 0  0   1   0  5    5    5   5    5    --  3   5   5                       1.25                                                                              0  0   0   0  4    4    4   4    5    3   --  3   3                   12  2.5 0  0   1   0  5    5    5   5    5    5   5   5   4                       1.25                                                                              0  0   0   0  4    5    4   4    5    4   2   4   3                   16  2.5 1  0   1   0  5    5    5   5    5    5   5   5   4                       1.25                                                                              0  0   0   0  5    4    4   4    5    4   3   5   3                   17  2.5 1  0   1   0  5    5    5   5    5    --  4   4   4                       1.25                                                                              0  0   0   0  --   5    5   4    5    --  --  --  --                  28  2.5 0  0   0   1  5    5    5   5    5    --  5   5   5                       1.25                                                                              0  0   0   0  --   5    5   5    5    --  5   5   4                   29  2.5 0  0   0   0  --   5    --  5    5    5   4   4   5                   31  2.5 0  0   0   0  5    5    5   5    5    --  3   4   5                   37  5   0  0   --  0  5    5    5   5    5    5   4   5   4                       2.5 0  0   1   0  5    5    4   5    5    5   --  5   --                  47  5   0  0   0   0  --   5    4   5    5    --  4   5   5                       2.5 0  0   0   0  --   5    --  5    5    --  4   5   4                   A   5   0  0   0   0  0    3    3   3    3    0   0   0   0                       2.5 0  0   0   0  0    0    0   0    0    0   0   0   0                   __________________________________________________________________________

Test Example 5

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of soybean, peanut, cotton, corn, sorghum, tall morningglory,common cocklbur, velvet-leaf, sicklepod, black nightshade, prickly sida,hemp sesbania, redroot pigweed, sun spurge, jimsonweed, commonlambsquarters, wild mustard, field bindweed, common purslane, fallpanicum, large crabgrass, green foxtail, barnyardgrass (Echinochloacrus-galli) and johnsongrass were sowed in 1 to 2 cm depth. A designatedamount of the test compound formulated in an emulsifiable concentrateaccording to Formulation Example 2, 3 or 6 was diluted with water andthe dilution was sprayed to the surface of the soil by means of a smallhand sprayer at a spray volume of 10 liters per are. The test plantswere grown in the outdoors for 20 days, and the herbicidal activity wasexamined. The results are shown in Table 10.

                  TABLE 10                                                        ______________________________________                                                   Herbicidal activity on Compound No. 16                                        Dosage (g/are)                                                     Weed         2.5           1.25                                               ______________________________________                                        Soybean      1             0                                                  Peanut       1             0                                                  Cotton       --            1                                                  Corn         1             0                                                  Sorghum      --            1                                                  Tall morning-                                                                              5             5                                                  glory                                                                         Common cocklebur                                                                           5             --                                                 Velvetleaf   5             5                                                  Sicklepod    5             4                                                  Black nightshade                                                                           5             5                                                  Prickly sida 5             5                                                  Hemp sesbania                                                                              5             --                                                 Redroot pigweed                                                                            5             5                                                  Sun spurge   5             5                                                  Jimsonweed   5             5                                                  Common lambs-                                                                              5             5                                                  quarters                                                                      Wild mustard 5             5                                                  Field bindweed                                                                             5             5                                                  Common purslane                                                                            5             5                                                  Fall panicum 5             5                                                  Large crabgrass                                                                            5             5                                                  Green foxtail                                                                              5             5                                                  Barnyardgrass                                                                              5             4                                                  Johnsongrass 5             3                                                  ______________________________________                                    

Test Example 6

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of wheat, pale smartweed, catchweed bedstraw, common chickweed,persian speedwell and blackgrass were sowed in 1 to 2 cm depth. Adesignated amount of the test compound formulated in an emulsifiableconcentrate according to Formulation Example 2, 3 or 6 was diluted withwater, and the dilution was sprayed to the surface of the soil by meansof a small hand sprayer at a spray volume of 10 liters per are. The testplants were grown in a greenhouse for 27 days, and the herbicidalactivity was examined. The results are shown in Table 11.

                                      TABLE 11                                    __________________________________________________________________________              Herbicidal activity                                                                   Catch-                                                                    Pale                                                                              weed                                                                              Common                                                                             Persian                                            Compound                                                                            Dosage  smart-                                                                            bed-                                                                              chick-                                                                             speed-                                                                            Black-                                         No.   (g/are)                                                                           Wheat                                                                             weed                                                                              straw                                                                             weed well                                                                              grass                                          __________________________________________________________________________    2     2.5 --  5   --  5    --  5                                                    1.25                                                                              1   5   --  5    --  --                                             3     2.5 0   5   3   5    5   4                                                    1.25                                                                              0   5   --  5    4   3                                              4     2.5 1   5   --  5    5   3                                                    1.25                                                                              1   5   --  5    3   --                                             5     2.5 --  5   5   5    5   5                                                    1.25                                                                              0   5   4   5    5   3                                              12    2.5 1   5   5   5    5   3                                                    1.25                                                                              0   5   5   5    5   --                                             16    2.5 1   5   --  5    5   4                                                    1.25                                                                              --  5   --  5    5   3                                              17    2.5 --  5   5   5    5   5                                                    1.25                                                                              0   5   5   5    5   4                                              18    2.5 --  5   5   5    5   3                                              27    2.5 1   --  5   --   5   --                                             28    2.5 --  5   5   5    5   5                                                    1.25                                                                              1   5   3   5    5   5                                              29    2.5 1   5   3   5    5   4                                                    1.25                                                                              0   5   --  5    3   --                                             31    2.5 --  5   5   5    5   5                                                    1.25                                                                              1   5   --  5    4   4                                              37    2.5 1   --  3   5    5   --                                             A     2.5 0   0   0   0    0   0                                                    1.25                                                                              0   0   0   0    0   0                                              __________________________________________________________________________

Test Example 7

Vat (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of corn, common cocklebur, velvetleaf, tall morningglory, blacknightshade and redroot pigweed were sowed therein and cultvated for 18days in a greenhouse. A designated amount of the test compoundformulated in an emulsifiable concentrate according to FormulationExample 2, 3 or 6 was diluted with water containing a spreading agent,and the dilution was sprayed over the foliage of the test plants bymeans of a small hand sprayer at a spray volume of 5 liters per are. Thetest plants were further grown in the greenhouse for 20 days, and theherbicidal activity was examined. At the time of the application, thetest plants were generally at the 1 to 4 leaf stage and a height of 2 to12 cm height, although growing stage of the test plants varied dependingon their species. The results are shown in Table 12.

                                      TABLE 12                                    __________________________________________________________________________              Herbicidal activity                                                              Tall            Black                                            Compound                                                                            Dosage morning-                                                                           Common                                                                              Velvet-                                                                            night-                                                                            Redroot                                      No.   (g/are)                                                                           Corn                                                                             glory                                                                              cocklebur                                                                           leaf shade                                                                             pigweed                                      __________________________________________________________________________    2     0.1 0  5    --    5    5   5                                            3     0.1 -- 5    5     5    5   5                                            4     0.1 -- 5    5     5    5   5                                            5     0.1 1  5    5     5    5   5                                            12    0.1 0  5    5     5    5   5                                            16    0.1 1  5    5     5    5   5                                            27    0.1 -- 5    5     5    5   5                                            28    0.1 -- 5    5     5    5   5                                            29    0.1 0  --   5     5    5   5                                            31    0.1 1  5    5     5    5   5                                            37    0.1 1  5    4     4    5   5                                            39    0.3 1  5    --    5    5   5                                                  0.1 0  5    --    5    5   5                                            44    0.3 -- 5    4     5    5   5                                                  0.1 1  5    --    4    5   5                                            45    0.3 1  5    --    4    5   5                                                  0.1 0  5    --    --   4   4                                            47    0.3 1  5    --    4    4   4                                            A     0.3 0  0    0     0    0   0                                                  0.1 0  0    0     0    0   0                                            __________________________________________________________________________

Test Example 8

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of wheat, ladysthumb, catchweed bestraw, common chickweed andpersian speedwell were sowed therein and cultivated for 18 days in agreenhouse. A designated amount of the test compound formulated in anemulsifiable concentrate according to Formulation Example 2, 3 or 6 wasdiluted with water containing a spreading agent, and the dilution wassprayed over the foliage of the test plants by means of a small handsprayer at a spray volume of 5 liters per are. The test plants werefurther grown in the greenhouse for 20 days, and the herbicidal activitywas examined. At the time of the application, the test plants weregenerally at the 1 to 4 leaf stage and a height of 2 to 12 cm height,although the growing stage of the test plants varied depending on theirspecies. The result are shown in Table 13.

                  TABLE 13                                                        ______________________________________                                                  Herbicidal activity                                                                               Catch-                                                                        weed  Common Persian                            Compound                                                                              Dosage          Ladys-                                                                              bed-  chick- speed-                             No.     (g/are) Wheat   thumb straw weed   well                               ______________________________________                                        3       0.1     --      5     5     5      5                                  4       0.1     1       5     5     5      5                                  5       0.1     1       5     5     5      5                                  12      0.1     --      5     5     5      5                                  16      0.1     1       5     5     5      5                                  34      0.3     1       5     5     4      5                                          0.1     1       5     4     --     4                                  42      0.3     1       5     4     --     5                                          0.1     1       4     --    --     5                                  A       0.3     0       0     0     0      0                                          0.1     0       0     0     0      0                                  ______________________________________                                    

Test Example 9

Seeds of corn, velvetleaf, redroot pigweed and black nightshade weresowed in the field as previously laid up in ridges and divided intoplots of 3 m². A designated amount of the test compound formulated intoan emulsifiable concentrate according to Formulation Example 2 or 5 wasdiluted with water, and the dilution was sprayed onto the soil surfaceby means of a small hand sprayer at a spray volume of 10 liters per are.The application was made with three repetitions. After cultivation for32 days, the herbicidal activity was examined. The results are shown inTable 14.

                  TABLE 14                                                        ______________________________________                                                    Herbicidal activity                                               Compound                                                                              Dosage           Velvet-                                                                              Redroot                                                                              Black                                  No.     (g/are)   Corn   leaf   pigweed                                                                              nightshade                             ______________________________________                                        5       1.6       0      5      5      5                                              0.8       0      5      5      5                                      16      1.6       0      5      5      5                                              0.8       0      5      5      5                                      B       8         0      2      1      5                                              4         0      1      1      4                                      ______________________________________                                    

What is claimed is:
 1. A compound of the formula: ##STR185## wherein Ris a hydrogen atom, a C₁ -C₅ alkyl group, a C₃ -C₄ alkenyl group, a C₃-C₄ alkynyl group, a halo(C₁ -C₄)alkyl group, a halo(C₃ -C₄)alkenylgroup, a halo(C₃ -C₄)alkynyl group, a C₁ -C₂ alkoxy(C₁ -C₂)alkyl group,a C₁ -C₂ alkoxy(C₁ -C₂)alkoxy(C₁ -C₂)alkyl group, a cinnamyl group, acyano(C₁ -C₃)alkyl group, a carboxy(C₁ -C₃)alkyl group, a C₁ -C₅alkoxycarbonyl(C₁ -C₃)alkyl, group, a halo(C₁ -C₅)alkoxycarbonyl(C₁-C₃)alkyl group, a C₁ -C₂ alkoxy(C₁ -C₂)alkoxycarbonyl(C₁ -C₃)alkylgroup, a C₁ -C₅ alkoxycarbonyl (C₁ -C₂)alkoxycarbonyl(C₁ -C₃)alkylgroup, a cyclo(C₃ -C₆)alkoxycarbonyl(C₁ -C₃)alkyl group, a C₁ -C₅alkylaminocarbonyl(C₁ -C₃)alkyl group or a di(C₁-C₅)alkylaminocarbonyl(C₁ -C₃)alkyl group and A is an amino group or anitro group.
 2. A compound according to claim 1, wherein A is an aminogroup.
 3. A compound according to claim 1, wherein A is a nitro group.